NL8203251A - METHOD FOR COMBATING INDUSTRIAL DECORATION WITH NITROIMIDAZOLE COMPOUNDS. - Google Patents

Description

N.O. 31,295 1

Process for combating industrial decay with nitro-imidazole compounds _______

The present invention relates to a method for combating industrial decay caused by obligate anaerobic sulfate reducing bacteria and to compositions for use in the method.

5 Industrial decay of liquid organic materials and aqueous liquids containing organic materials caused by the growth of microorganisms that metabolize organic matter with the simultaneous formation of harmful metabolites is a widespread problem in many branches of industry This growth of microorganisms requires the presence of free water in liquid organic material, for example an oil, since although the microorganisms can often go into the organic, for example, oil phase, their growth and activity are largely limited to the water phase. It is practically impossible to exclude from liquid organic material the small initial amounts of water required for the initiation of the growth of microorganisms, and in fact water in larger or smaller amounts is deliberately absorbed into many liquid organic materials used in industry. A wide variety of bacteria, fungi and yeast are encountered in the decay of liquid organic materials, and it is also virtually impossible to exclude all such microorganisms outside of the liquid organic materials. Examples of liquid organic materials and aqueous liquids containing organic materials that are subject to industrial decay caused by the growth of microorganisms are petroleum hydrocarbons and vegetable oils and liquid products containing them used in industry, including fuel oils, lubricating oils and mineral oil-based hydraulic fluids, oil-in-water emulsions, for example, metal working fluids, water-in-oil emulsions, for example, hydraulic fluids of the water-in-oil emulsion type, and Various solutions and emulsions of glycols, which are used as metal working fluids * 35 Other aqueous liquids, containing organic materials, which are subject to serious deterioration caused by the growth of microorganisms, are water-based paints, paper pulp 8203251 2 4 * sulfite processing fluids and even liquids, which are largely inorganic are, for example, process water, electrolytic coating solutions and oil well injection water. Industrial decay of liquid organic materials and aqueous liquids containing organic materials, for example petroleum hydrocarbons and vegetable oils, caused by the growth of microorganisms, can result in corrosion of metal storage tanks, for example in the storage of fuel oils and in the extraction and processing of mineral oils and metal workpieces, for example in the machining, drilling, grinding and grinding of metals, when decay occurs in metalworking fluids used as lubricating oils and coolants during metal processing, in the degradation of additives in lubricating oils with subsequent deterioration of the lubricating properties of the oils, in the reduction of sulfonate and sulfate emulsifiers and the oxidation or reduction of nitrogen-containing emulsifiers and corrosion inhibitors with subsequent deterioration and non-stability of oil-in-water and water-in-oil emulsions, e.g. the reduction of the oil-water interfacial tension upon stored fuel oil with subsequent failure of oil-water separation and contamination of the fuel oil by water and the blockage of conduits, filters and openings by the bodies of the microorganisms.

Oxygen levels in liquid organic materials and aqueous liquids containing organic materials, for example petroleum hydrocarbons and vegetable oils and liquid products containing them, used in industry are often low and can be further reduced by the growth of aerobic and optional anaerobic microorganisms favoring the growth of obligate anaerobic sulfate reducing bacteria (the term "obligate anaerobic sulfate reducing bacteria" as used herein refers to obligate anaerobic bacteria capable of extracting metabolic oxygen from compounds containing sulfur in an oxidation state and leaving it in a reduced state, usually reducing hydrogen sulfide, or metabolic elemental sulfur to hydrogen sulfide). Examples of obligate anaerobic bacteria that cause industrial decay are Desulfovibrio desulfuricans, Desulfovibrio gigas and Desulfotomaculum nigrificans k0 (Clostridium nigrificans or Desulfovibrio orientis). Bond 8203251 + 1? Anaerobic sulfate-reducing bacteria reductively metabolize sulfates and sulfonates, for example sulfate and sulfonate, containing emulsifiers, for example, alkyl sulfates and alkyl aryl sulfonate emulsifiers, and sulfurized oils and fats and free sulfates, which are present in water. release of hydrogen sulfide and result in particularly serious problems for industries! " decay in liquid organic materials and aqueous solutions containing organic materials, e.g. petroleum hydrocarbons and vegetable oils, e.g. fuel oils and lubricating oils, mineral oil-based hydraulic fluids, oil-in-water emulsions, e.g. metal working fluids, water in-oil emulsions, for example hydraplic liquids of the water-in-oil emulsion type and aqueous solutions and emulsions of glycols, which are used as metal working liquids, with the production of stench and corrosion caused by the liberated hydrogen sulfide and degradation of emulsifiers, with subsequent deterioration and instability of the emulsions. Similar problems of industrial decay caused by obligate anaerobic sulphate reducing bacteria are encountered in paper pulp sulphite processing fluids, water-based paints, oil well injection water, process water, electrolytic coating solutions, in closed water circulation systems, for example heat exchangers and cooling and heating water systems, storage and delivery systems of hot water and in water seals of gas containers used for the storage of hydrocarbon gases. Decay caused by obligate anaerobic sulfate-reducing bacteria is a particularly difficult problem in the water, which collects in fuel oil tanks and in oil well injection water.

30 Oil-in-water emulsion-based metalworking fluids and aqueous solutions and emulsions of glycols used as metalworking fluids, for example, machine tool coolants and metal rolling coolants containing mineral or vegetable oils or glycols, emulsifiers, corrosion inhibitors and water containing, if desired, fats, soaps and small amounts of special additives that serve as film plasticizers, anti-foaming agents and high pressure additives are known to be widely used for cooling and lubrication purposes in metalworking operations. These fluids 40 perform a number of functions in metalworking, including 8203251 * · including lubrication and temperature reduction at the machining interface of the tool, promoting tool life and removing chips and shavings. metal working area and cooling of the metal sheet during the rolling and pressing operations. For economic reasons, it is essential that the metal working fluid be kept in a recirculation system so that the fluid can be reused repeatedly. Such metalworking fluids usually contain about 1 to about 15 vol. Of oil and / or glycols and are used at tera temperatures just above ambient temperature up to 200 DEG-60 DEG. Therefore, coolants for the metal processing at temperatures just above ambient temperature are used and their oil and / or glycol content varies from about 1% in grinding coolants where heat dispersion is maintained to maintain the dimensional accuracy of the first it is important, up to about 15% in heavy machining, where lubrication is an essential requirement, while coolants for metal rolling usually have an oil and / or glycol content of 2 to 5 vol. and effective are at higher temperatures which are often if0-60 ° C. These metalworking fluids are easily subject to industrial decay due to the growth of microorganisms and their oxygen content tends to be very low, especially when the fluid is not in use. This promotes the growth of obligate anaerobic sulfate reducing bacteria, resulting in serious industrial decay problems caused by the degradation of alkyl sulfate and alkyl aryl sulfonate emulsifiers, the breaking of the emulsions, free oil release and corrosion and stench caused by the release of hydrogen sulfide. Accordingly, the control of industrial decay caused by the growth of obligate anaerobic sulfate reducing bacteria is of great importance in the recirculation and reuse of oil-in-water-emulsion type metalworking fluids and aqueous solutions and emulsions of glycols, which when metalworking fluids are used.

35 Attempts have been made to combat industrial decay caused by the growth of microorganisms through the uptake of many biocides, but the properties required for a satisfactory biocide are extremely demanding and relatively few have been used commercially with sucrose. Therefore, a bio-ifO cide, to be used to combat industrial 8203251 5 "" 7 - ^ * ·; ·· ”·; · Ψ *? · Spoilage caused by the growth of microorganisms, in addition to being effective in killing or inhibiting the growth of the microorganism, desirably be non-toxic and non-irritating when used, to have sufficient stability for 5 suitable time period, at the appropriate temperature ranges and pH ranges, preferably to be soluble in water to give an appropriate concentration in the aqueous phase, where the growth of microorganisms takes place and not preferably are soluble in the oil or organic phase, compatible with the system 10 in question, for example, without adverse emulsion properties and.

bring about stability, weaken foaming or flotation φ or even the pH of the system and, if used in fuel oils or in metalworking, undesired surprises with combustion substances, such as phenols, for example p-chloro-m cresol 15 and phenol, heavy metals, formaldehyde releasing compounds and other biocidal active compounds have been commercially used to combat industrial decay caused by the growth of microorganisms with varying degrees of success and safety when using many of them As a result, there is a continuing need for new methods of combating industrial decay caused by the growth of microorganisms, more particularly against decay caused by the growth of obligate anaerobic sulfate reducing bacteria.

It is known that 1- (2-hydroxyethyl) -2-methyl-5-nitroimidazole (hereinafter referred to as "metronidazole"), 1,2-dimethyl-5-nitroimida sole (hereinafter referred to as "dimetridazole"), 1 - (2-Hydroxypropyl) -2-methyl-5-nitroimidazole (hereinafter referred to as "secnidazole") and 1-methyl-2-isopropyl-5-nitroimidazole (hereinafter referred to as "ipronidazole") are effective against protozoa, amoebae and certain anaerobic bacteria, which can infect humans and animals, Bond anaerobic sulfate reducing bacteria are not a recognized cause of infections in humans and animals and it has not been hitherto suggested that the compounds mentioned above would be effective against obligate anaerobic sulfate reducing bacteria in human or animal medicine, nor that they would be effective in combating industrial decay caused by the aforementioned bacteria. Metronidazole, dimetridazole, secnidazole and ipronidazole would therefore not themselves be suggestions 40 for those seeking new avenues for combating industrial decay caused by such organisms, nor would it be clear that the compounds have the coraboration of other properties necessary to be successfully used to combat industrial decay.

As a result of research and experimentation, it has surprisingly been found that the nitroimidazole compounds dimetridazole, metronidazole, secnidazole and ipronidazole can be used to combat the growth of obligate anaerobic sulfate-reducing bacteria in liquid organic materials containing or aqueous liquids containing organic materials. It will be understood that the term "nitroimida sole compounds" as used herein refers to dimetridazole, metronidazole, secnidazole and ipronidazole. Accordingly, as a feature of the present invention, there is provided a method of combating industrial decay of those liquid organic materials containing water or aqueous liquids containing organic materials subject to decay caused by the growth of obligate anaerobic sulfate-reducing bacteria, for example, petroleum hydrocarbons and vegetable oils, and liquids used in industry containing them, for example, fuel oils, lubricating oils, mineral oil-based hydraulic fluids, oil-in-water emulsions, for example, metal working fluids, water-in oil emulsions, for example hydraulic fluids of the water-in-oil emulsion type, aqueous solutions and emulsions of glycols used as metal working fluids, paper pulp sulphite processing fluids, water-based paints, oil well water, industrial process water, electrolytic solutions covers, sealed water circulation systems, storage and hot water delivery systems and gas seal water seals used for the storage of hydrocarbon gases, which include the aqueous phase of liquid organic materials containing water or aqueous liquids containing organic materials to contain an amount of at least one nitro-35 imidazole compound of the present invention sufficient to prevent the growth of obligate anaerobic sulfate reducing bacteria. The concentrations of the nitroimidazole compound (s). which can be used individually or in combination according to the present invention generally lie between 100 ppm and 500 ppm and more particularly 100 ppm of the total 8203251 volume of the liquid organic material containing water or the aqueous liquid, containing organic materials to be protected from industrial decay caused by the growth of obligate anaerobic sulfate reducing bacteria, but lower or higher concentrations can be used according to the particular problem of industrial decay in question and can be easily determined by an appropriate test.

The nitroimidazole compounds are not preferentially · soluble in the organic phase of the liquid organic materials, containing water and aqueous liquids containing organic materials, and are sufficiently soluble in their aqueous phase to give concentrations effective at preventing the growth of obligate anaerobic sulfate reducing bacteria, non-toxic and non-irritating in use, 1.5 unlike most agents which have hitherto been used to combat industrial decay caused by the growth of microorganisms, have sufficient stability for a suitable period of time at the appropriate temperature and pH ranges, do not affect the emulsion properties and stability of oil-in-water and water-in-oil emulsions, do not cause foaming or flotation, or influences the pH itself and does not produce any unwanted ash when burned.

The nitroimidazole compounds of the present invention can themselves be added to the liquid organic materials containing water or aqueous liquids containing organic materials which are desirably protected from industrial decay by the growth of obligate anaerobic sulfate reducing bacteria. but are preferably added in the form of solutions, suspensions or emulsions in suitable solvents, for example water, glycols, for example ethylene glycol, ethyl oxalate, dimethylformamide, dimethylacetamide, liquid hydrocarbons, for example gasoline and mixtures thereof which, if necessary, may contain one or more surfactants. An illustrative example of a suitable formulation is a suspension prepared by mixing microfine dimetridazole (25 w / v / O, Texofor M6 '(4 w / v), Arylan CA (6 w / v) vol. ^), Attagel 50 (1.0 w / v%) and petrol (odorless) to 100 vol.

Texofor H6 is an ethoxylated oleic acid, containing 6 moles of ethylene-40 oxide per mole of oleic acid; 8203251 δ \

Arylan CA is calcium dodecylbenzene sulfonate;

Attagel 50 is an intumescent attapulgite clay.

According to a preferred feature of the present invention there are provided metalworking concentrates which, after dilution with water, are suitable for the preparation of metalworking liquids containing oils and / or glycols, emulsifiers and corrosion inhibitors which are customary in concentrates used for the preparation , by dilution with waterivan metalworking fluids and an amount of nitroimidazole compound (s) 10 sufficient to give the desired concentration of nitroimidazole enhancement in the metalworking fluid after dilution with water and generally about 0.05 to 5 wt. /vol.$ nitroimidazole compound (s).

If desired, the nitroimidazole compounds of the present invention may be used in conjunction with known industrial decay control agents caused by the growth of microorganisms, eg phenols, eg p-chloro-m-cresol and phenol, heavy metals and formaldehyde releasing compounds , in the process of the present invention to combat industrial decay caused by the growth of bondate anaerobic sulfate reducing bacteria in liquid organic materials containing water and aqueous liquids containing organic materials. The nitroimidazole compounds of the present invention will also combat liquid industrial decay caused by nitrate reducing bacteria in liquid organic materials containing water and aqueous liquids containing organic materials.

The valuable properties of the nitroimidazole compounds of the present invention in combating the growth of obligate anaerobic sulfate reducing bacteria in liquid organic materials containing water and aqueous liquids containing organic materials that are subject to decay caused by the growth of obligate anaerobic sulfate-reducing bacteria are illustrated in the following 35 experiments-1 to k · 8203251 9

Experiments 1 to k

Activity against obligate anaerobic sulphate reducing bacteria. Lemming the growth of obligate anaerobic sulphate reducing bacteria.

5 Test method (I) for obligate anaerobic sulphate reducing bacteria

The test compounds were taken up by the addition of the appropriate amounts of aqueous solutions containing 5 ppm of di-metridazole or metronidazole at concentrations of 50, 100, 250 and 500 ppm in an oil-in-water emulsion, which is known to be heavily contaminated with obligate anaerobic sulfate reducing bacteria. Samples of the contaminated oil-in-water emulsion to which no test compound had been added were used as a control. Samples of the contaminated oil were taken immediately after addition of the test compounds and after 3, 5 and 2 hours.

Iron sulfite agar (Oxoid Ltd) was prepared and iri tubes (10 ml) poured. The tubes were sterilized by autoclaving at 103 kPa pressure for 15 minutes and sealed with Astell caps, ensuring an airtight seal and consequently anaerobic growth. The tubes were placed in a water bath at 50 ° C, which maintained the agar in the liquid state. An eyeful (1-50 ml) of the samples of bacterially contaminated oil-in-water emulsions were then used as an inoculum and the tubes were incubated at 37 ° C for 5 days.

The effect of the test compounds on obligate anaerobic sulfate reducing bacteria present in the contaminated oil-in-water emulsion was noted as follows: 30 +++++ completely black - no inhibition ++++ good growth, but not completely black + ++ black / gray spots of inhibition and growth ++ gray with black dots + transparent, except for some black dots 35 0 transparent, complete inhibition

The following results were obtained: 8203251 * * EXPERIMENT 1 (a) Metronidazole

Concentration Contactti.id with metronidazole of metronidazole Immediate 3 hours 5 hours 2k hours 0 (control) +++++ +++++ +++++ +++++ 50 ppm +++++ ++++ + +++ ++ 100 ppm +++++ +++++ ++ + 25Ο ppm ++++ +++ + 0 500 ppm +++ +++ 0 (b) Dimetridazole

Concentration Contactti.id with dimetridazole of v ··· - ·. - dimetridazole Immediate 3 hours 5 hours 2k hours 0 (control) +++++ +++++ +++++ +++++ 50 ppm +++++ ++++ ++++ +++ 100 ppm ++++ +++ ++ + 230 ppm ++++ +++ 0 500 ppm +++ + 0 0 EXPERIMENT 2 (a) Metronidazole

Concentration Contactti.id with metronidazole of metronidazole Immediate 3 hours 5 hours 2k hours 0 (control) ++++ ++++ ++++ ++++ 100 ppm ++++ +++ + + 200 ppm ++ ++ +++ + 500 ppm +++ ++ 0 8203251 * * 11 (b) Dimetridazole

Concentration Contact tid with dimetridazole of dimetridazole Immediate 3 hours 5 hours 24 hours 0 (control) ++++ ++++ ++++ ++++ 100 ppm ++++ +++ + 0 200 ppm ++ + + 0 0 500 ppm +++ 0 0 0 EXPERIMENT 3 (a) Metronidazole

Concentration Contactti.id with metronidazole of. metronidazole Immediate 3 hours 3 hours 24 hours 25 ppm ++++ +++ +++ +++ 50 ppm ++++ +++ +++ +++ 100 ppm ++++ +++ + + ( b) Dimetridazole

Concentration Contact tid with dimetridazole of dimetridazole Immediate 3 hours 5 hours 24 hours 15 ppm ++++ +++ ++ ++ 50 ppm ++++ +++ ++ ++ 100 ppm ++++ +++ + + EXPERIMENT 4 Test staple method (11) 1

Flasks containing 100 ml of aqueous solutions, each containing 50 * 100, 250 or 500 ppm solutions of the test compound, were treated with an oil-in-water emulsion (0.1 ml), 5 of which are known that it is heavily contaminated with obligate anaerobic sulphate-reducing bacteria. A control flask containing no test compound was also prepared. Samples from the control flask were taken immediately after addition of the oil-in-water emulsion and from all flasks after 3-5 hours and 48 hours.

Iron sulfite agar (Oxoid Ltd) was prepared and poured into tubes (10 ml). The tubes were sterilized by autoclaving at a pressure of 103 kPa for 15 minutes and sealed with Aster caps, which ensure an airtight seal and consequently allow anaerobic growth. The tubes were placed in a water bath at 50 ° C, which maintained the agar in a liquid 8203251 12. A ccgrcL (1/50 ml) of the sample of bacterially contaminated oil-in-water emulsions were then used as an inoculum and the tubes incubated at 37 ° C for 7 days. The effect of the test compounds on obligate anaerobic sulfate-reducing bacteria present in the contaminated oil-in-water emulsion was noted as described above. The following results were obtained: 8203251 13 φ © β + hi - 3 + 3 ί 4- + CO + + CO + + + + Ο Ο O .. - + + + Ο Ο Ο β β φ β + hi 3 + 3 + 4 * + + + _3 * + + * 4 * 4 * 4- _ _ f \ J + + + Ο Ο CM + + +00 £ j ^ 0 4 * © + β + + hit β + + + 3tt.

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βω ω • rl · Η Η χ -pos ε ε ε Ο φ ρ <* + 3 .S1 3 Τίββ + 5¾¾1¾¾ ο -Ρ £ ΰ PS Pi _ _ or S> -riO οοοοο φ X ο ΙΓ \ Ο ΙΑ Ο Ο Ο Λ | 1Λ [Ν Ο / -Ν η ό ^ & Q 0 ο W ο Ρ3 8203251 17

Kathon MW886, Grotan TK2 and Bodoxin are commercially available industrial biocides used to combat contamination by obligatory anaerobic sulfate reducing bacteria.

The results obtained in Experiments 1, 2, 3 and k confirm that metronidazole, dimetridazole, ipronidazole and secnidazole inhibit sulfide production by obligate anaerobic sulfate-the bacteria, with the effective concentration in these experiments 1 to if is about 100 ppm. The effective concentration of Kathon MW886, which can cause severe shroud and eye irritation, is also about 100 ppm. For Grotan TK2 and Bodoxin, the effective concentration is higher, at about 500 ppm.

The compatibility of nitroimidazoles of the present invention with oil-in-water emulsion metalworking fluids. 15 prepared from commercially available metalworking concentrates is illustrated in the following experiments 5 to 8, wherein the commercially available metalworking concentrates are: Concentrate A: a general purpose cutting oil emulsion used at a concentration of 2 to 5 vol / vol .%; 20 Concentrate B: A general purpose cutting oil used at a concentration of 1 to if vol / vol. #;

Concentrate C: an aluminum rolling oil, which does not become stable at the "bite" of the rollers and improves later, used at a concentration of 5 vol / vol. Concentrate D: a partially synthetic cutting oil formulation, used as a cutting oil at a concentration of 1 to 2 vol / vol. #; Concentrate B: a general purpose cutting oil used at a concentration of 3 to 5 vol / vol. ^;

Concentrate F; a cutting oil used for machining 30 kV / grade, used at a concentration of 3 vol / vol.

Concentrate G: a non-oil based synthetic grinding fluid used at a concentration of 2 vol / vol. 3. EXPERIMENT 5 Emulsion Stability 35 Cutting and rolling oils used in the form of oil-in-water emulsions should maintain emulsion stability in use. This experiment is designed to determine the stability of such oil-in-water emulsions by recording the tendency of oil droplets to coalesce, which is a feature of instability. ifO Oil-in-water emulsions containing commercially available oil 8203251 18 concentrates were prepared by the following method [Institute of Petroleum Standard Test (IP) 263-70]:

Distilled water and the oil concentrate were brought to a temperature of 20 ° - 4 ° C separately before merging took place 5. The appropriate volume of water was stirred in a 500 ml conical flask, using a magnetic stirrer, at a speed sufficient to create a vortex just deep enough to reach the bottom of the flask. The appropriate volume of oil concentrate and the appropriate volumes of a solution containing 5000 ppm of metronidazole, dimetridazole or ipronidazole in water to 50, 100, 250 and 500 ppm of metronidazole, dimetridazole or ipronidazole in the oil-in-water emulsion (total volume ^ 200 ml) were then quickly added from a hypodermic syringe (without needle) and stirring was continued for 2 minutes after the additions were complete. Oil-in-water emulsions containing no nitroimidazole compound were formulated in a similar manner to control runs. The oil emulsion was then stored at ambient temperature for 24 hours.

A sample of the oil emulsion thus obtained was diluted 1: 2000 with Steriflex No. 1 saline (Allen and Hanbury's Ltd) and the "too large" oil droplet size distribution in a 0.5 ml sample of this dilution was determined using a Coulter counter (100 µm opening) (Coulter Electronics 25 Ltd) connected to a P64 analysis device and layout. The oil-in-water emulsions were then stored for 7 days and the oil droplet size distribution was redetermined using the same Coulter counter setting so that direct comparisons could be made. As is normal with oil-in-water emulsions, which have been left untouched for several days, separation in oil, rennet and cream had occurred between the two determinations, and prior to sampling for the second assay, the flasks were separated. shaken for seconds, rotated alternately clockwise and counterclockwise.

The following results were obtained: (a) Oil-in-water emulsion containing 2 vol / vol, concentrate A 3

Metronidazole: An increase in drops of 2-5 µm at 100 ppm of metronidazole after 7 days indicates very little instability of the emulsion.

Dimetridazole: The emulsion stability after 7 days was slightly improved, especially at 50 ppm dimetridazole.

Ipronidazole: No significant decrease in the emulsion stability ward after 7 days was observed.

(b) 01-in-water emulsion containing 1 v / v concentrate B 5 Metronidazole: the emulsion stability after 7 days was slightly improved.

Dimetridazole: Slight instability after 7 days in the oil-in-water emulsion containing 250 ppm dimetridazole was determined. Ipronidazole: No significant change in emulsion stability was observed after 7 days.

(o) Oil-in-water emulsion containing 5 vol / vol. concentrate F Metronidazole: No change in emulsion stability was observed after 7 days.

Dimetridazole: No change in the emulsion stability after 7 da-15 gene was observed.

(d) Oil-in-water emulsion containing 5 vol / vol% concentrate E Metronidazole: a slight increase in emulsion stability was observed after 7 days of stirring.

Dimetridazole: The emulsion stability after 7 days was within satisfactory limits.

Ipronidazole: A very slight decrease in emulsion stability was observed after 7 days.

(e) Oil-in-water emulsion containing 1 vol / vol concentrate D Metronidazole: No change in emulsion stability was observed after 7 days.

Dimetridazole: A slight increase in emulsion stability after 7 days was observed.

Ipronidazole: A very slight decrease in stability after 7 days was observed with the oil-in-water emulsion containing 250 ppm iproni-50 dazole.

(f) Oil-in-water emulsion containing 2 vol / vol concentrate G Ipronidazole: no significant change in emulsion stability was found after 7 days.

(g) 01-in-water emulsion containing 2 vol / vol concentrate C Metronidazole: no change in emulsion stability was found.

Dimetridazole: No change in the emulsion stability was observed.

Ipronidazole: a very slight decrease in the emulsion stability ifO was observed after 7 days.

8203251 20

The results show that the recording of metronidazole, dimetridazole and ipronidazole at concentrations of 50, 100, 250 and 500 ppm in the oil-in-water emulsion had no significant adverse effect on emulsion stability.

Experiment 6

Corroding ability

This experiment is designed (IP 287/7 ^) to determine the ability of oil-ice-water emulsions to prevent rusting of machines and assemblies during manufacturing operations, 10 by the following method:

Cast Iron Shavings (Herbert Machine Tools Ltd. P.0. Box 50,

Edgweck Works, Coventry, England) were washed in acetone (reagent quality) and dried in a hot oven at 1 + 8 ° G. During washing, the chips were not touched by hand. When the chips were dry, they were sieved on a 25 mesh screen, removing material passing through the screen.

A circumferential line of 35 mm square was drawn in pencil in the center of a filter paper (Whatman No. 5 »Qualitative, 90 mm), which was then placed on the bottom of a petri dish. Using a spatula and a mold, the marked 2 mm area was then covered with a single layer of chips.

The mold was then removed and 2 ml aliquots of oil-in-water emulsions (prepared according to the method described in Experiment 5) containing a range of ratios of oil concentrates were pipetted onto the chips so that the entire surface of the petri dish was covered and the chips were thoroughly wetted. A lid was placed over the petri dish. After 2 hours, the filter paper was removed from the dish, washed with tap water and dried. A transparent grid was then placed over the test surface of the circumference of 35 π® on the dry filter paper and the staining area was expressed per percentage, In order to facilitate the determination, the percentage of colored area should be greater than 10 % and less than 60% 1 The dilution of each oil concentrate, where there was a substantial increase in colored area (known as the "breakpoint") was determined. For each oil concentrate, a series of oil-in-water emulsions containing the breakpoint ratio of oil concentrate and 50, 100, 250 and 500 ppm metronidazole, dimetridazole or ipronidazole were prepared and ifO each of the oil-in-water Emulsions were tested according to the above-described method 8203251 21.

The following results were obtained.

(a) Oil-in-water emulsion containing 2 1/2 vol / vol% concentrate A

Concentration Colored surface expressed as a nitroimidazole percentage_ (ppm) Metronidazole Dimetridazole 0 (control) 8 2 50 10 k 100 10 6 250 1 8 500 0 10

A slight decrease in the colored surface was observed at 250 ppm and 500 ppm of metronidazole. Repeated experiments confirmed this observation. A slight increase in the colored surface was observed with dimetridazole. 1 8203251 22 Η ο ο Ν β β • Η Ρ -Ρ φ ε • Η η β 0) η.

Ο Η Η Ο Ο Ο ta ο φ ο φ (d Ν be Ν h £ β Λ Cd β β · Η ΙΑ Ο Ο Ο Ο Ό -Ρ Ό +3 β V £) ν £) VO -β- LA · Η S · Η

β Ο β · ® S

φ β Ο Η Ο Ο Ο Pi β Ο β β β η -μ ο Φ +3 φ Φ Ν Ρ Η Φ ρ. ε β ο ε β β ο β Η · Η Φ t5 Η φ 'Φ S3 Φ β Φ φ £ Ο β> Ο β Μ · Η ο [Q Ν Ρ γΗ β Ο Ο Ο Ο Ο Ν Η · Η β -Ρ C \ Jf \ JOJ-3-LP> cd +) φ -Ρ η φ -μ -ρ · ε φ +3 0 ε φ id · π ε χ ο ε 3 «+3 β Ν β +3 β β βββ Φββ 'β Φ> β β ε φ> φ ε φφ · η ο ε φ be ο, Π he β ΙΑΟΟΙΑΟΟβΟΑ-Ρ β 4343.: ΓΓηΐΙΛ · ί Φβ · Η φ

(ΗΦ · ΗΦ ho Φ Ο β bO

β 8 β bO Ρ +3 Η β β -Ρ>! β cd ^! P ββββ β cd cd 5 cd cd Η ρ +3> "β +3 β β β β β β Φ β φ φ Φ β Φ Ρ Φ ο ρ. & Φ Ο Ρ> β ρ ^ β ο ο ο λ: ο χ υ cd X ο β Η β β Η β β ο Η "SR β Η> Η ^ β ο> • β Ο β>» Φ «β ΗΦΟ Φ β Η Η β Φ ΟΗΝ ρ φ Ο ^ β Ρ <> 3 S Ρ Ρ> Φ · Η Ο Ο Ο Ο Ο Ρ \ φ β Ο Ρ \ Ο β ΙΑ VO ΙΑ IN CN Ο Η C5 Ή Ο Η Ο Ο β 'ΙΑ Ο Ο ΙΑ Ο Φ Ο β Φ> Ο · ΓβΙ ^ ϊΛ4 * β «> -Ρ ^ ρ ρ β Φ β -3 +3 β β ια 2 Ρ φ φ β φ φ s Η Η Φ Η Η Λί Η · Η dd β Φ .id Ό Φ

60 Φ bO

·· Μ · φ +3 Φ · Ρ • Η Φ -Ρ · Η Φ

[Q rC Φ to rP

β β β β ε η β ε · ρ φ / λ · Η Θ ^ ι ε φ ι ε φ β ρ ε φ β Ρ) ε φβ β ε φ 'ο β · +3 ββ + 3 ^ βΗ

Cd φ β β ^ Φ ο & Η ΟΡ5ΗΦ ΟΟ | Ο +> βΙΟΗ -Ρ 2 ΰφΟΦ β Φ Ο Ο β • Η · Η S Η φ φ · Η · Η «β Φ β Ι + Jcd Ο h0 bO I +3 aS +3. bO Ή Φ cd β ΟβΟΟΟΟ ββ φφβ Ο β Ο Ο Ο Ο β Ρ ιρ | β · Η +3 Α ο ΙΓΝ Ο · Η · Η · Η β * Η Ο ΙΑ Ο ΙΑ Ο · Η +>. Η +3 ε β ν ~ CM ΙΑ β β Η +> ε υ <-ΓΜΙΛβΦ Ο β · Η ο Φ Φ Ο β · Η ^ Φε ΦΟΟ bO bO Φ Ο bO · Η Ο β - 'Ο β - ^' - 'β + 3 β β * * β * Ρ mri Δ ο · Η Φ Φ Ο Ο · Η Φ β w ο Ρ Η Η ^ Ο β & 3Φ 8203251 <<23 60 d Ρ η fn Ρ β Φ I — I β X Φ Ρ β β • Η Ο> Φ Φ ε 60 * β Η S3 60 Ο ® α ο Ο -Η 2 -Ρ β ® _j β φ Ο »φ Φ Φ · Η 6 £ Ο 60 Η 6C k (Ο Ν Ο 1Λ! Λ Ο Λ 3 Μ tO +? Ρ β ΙΛ Ν 1Λ 1Λ r Ή -Ρ ® β Φ β β 5 5 φ ρ Φ Η φ £ Φ β 60 ϋ ^

Sn Ο φ Μ Φ β β 8 ® j * Ρ- ft ® g · ρ · Φ Η Φ β rj Φ £ Μ Φ - ο ω ο -3 44 ® 3 Ν ου ο φ ω ο «5 Η Ν 60 Η Ν ^ β β β (0 Φ · Η β ρ ^ 3 Ρ X, ρ β Ρ ιΗ Α Ο Α Ο Α Ο L ·! β φ ^ 4 β -tj “OJ β * ΙΑ (Μ β ρ 3 Η Ο 60 Ρ β -Ρ +?

β β Ο ^ ® S

> · Ρ ο ρ β> τ> ε = ΦΦΝ ΦΦ ΦΦ-Η, Ώ 6C β Α Ο Ο Ο Ο S ® «« Η Ρ -Ρ AA Α ^ _ £ φ Q ρ ρ Ρ Ό W Ή% β β Φ β Ρ Ο ρ ρ ε φ ρ Ν to Λ! ® Ρ β β ε 3 '«5 Ρ JS ^ (. Η · Η Η Η 8 β Η ~ _μ *> ρ Φ Ο ft Ρ> ε β ^ ρΟ'ΟβΡ

φ ο to tg φ φ S.

or j. φ β Ο Φ ft ® β ρ. 60 · β Ο ft ft ε οο ρ Ρ Α Ο Ο ο ο ® β Ο £ Ό to Ο β Ό ® * ο β ί> β ® ^ β • 3 ft *? £ η Φ Ό Ή Ο Η Φ «Ο Η Η β Α Ο Η Η ®> ΡΟ ® Ρ OJ> Λ Ο ^ \ φ Ο 5 Φ \ Φ Ο Η0» § ΟΟΟΟ Ο60ΒΟΟΰβ ο Ο Ο Ο Ο β ° .ρ Ό -ί to (Λ ^ ® ρ Ρ Η · Η ^ CM β β Ο η A ft. „^ Ο β ο ρ ο Μ <η £ j Ο & 3 Φ k μ • Η Ρ Η β Ή -Ρ Τ1

Ρ®, ¾ -p φ Ρ Φ U

X β · Η ε S 3 '»© β β · Φ Φ> ρ β Φ Η

, _j ρ Φ Ρ ρ X

[Q CQ ε to Μ.

γ- | Φ · Η Η 5 Ρ ο Ό φ β -Η ε ρ 6ο ε Λ, φ ^ Ρ β Φ φ I g β φ η ι ε, rj pft ρ ε β β ft · £ φ · Ρ Φ Φ “β to ρ ^ Μ β 60 ρ ^ · Η β / -¾ β Η Φ ^ Μ fe_j Φ · Η Φ β. S Η Φ β 1 Ο ι — I βΡΦΙ Ο Η> βΦΟ Ο φφΦβΦΟ Ο Ρ Ρ Ν β Ό Φ Ρ Ρ Ν U Φ ιρβ ρ β 60 ft I Ρ Φ -Ρ Μ Φ β Τ3 ΟβΟΟΟΟ β-Ρ ® ΦβΌ β Ο Ο Ο Ο β • Η U Ρ Ο ΙΑ Ο ΙΑ Ο β CQ Η β Ρ Ο Α Ο Α Ο Ρ ΗΡΕ Φ * -C \ JA Φβ8 ΗΡε Φ r-OJASn φ ο 'β Φ ο Φ β β Ό φ β ^ / - \ βρ ΦβΟ ^ βρ 5 POP φ φ Ο φ Ο Ρ φ woe ϋί ^ - ^ οβ w 8203251 24 i 3 Φ • -μ cd φ s Ό I • ft · | "Ϊ · Η • Η I, £ Φ • Η Η Η Ο Ο Ο Φ Φ Ν Φ b £ be cd -P cd (ΰ Td Λ -p

+ J · Η Ο S

S 3 Ο Φ

P -P N O

Ο φ 3 3 3 E Φ Φ Φ Η · Η Td ft

ft O 'ft S

0 OS

S N S Φ φ td Φ Φ Φ φ Ό Ό

• Η H tQ

CQ 3 Ο ΙΑ Ο ΙΓ \ 1Λ O S H

H-p c \ j oj fft (Λ -ft o cd cd H

td Φ n> o + s S cd -P -P o · cdAJ'H Td S cd S3 N £> 30 · Η Φ> 3. Cd ® φ 3 3 ρ, φ 3 ft e

ore Oft Ο ft · Η ΙΓ \ ΙΛ ΙΛ fft N> O

<u 3 cd φ S r- 3

HbC -p Λ o & c Ο φ Φ o -p 3 be -Ρ -Η SW -P Ή ft 3 cd ss cd sh 5 cd +> φ cd <dh Μ φ bo 3 X s • p td S -H -p cd S Η Φ SH ¥ φ> s φ> os td φ o 3 ® 3 Φ H cd> S ® ^ O ft Ο Φ o ft 0 ft O bO-HOft .¾ ON S to o id -2¾. cd -H ο ^ • td ft 3 3 · ft

H 3 vH ΙΛ Ο ΙΛ Ο O 0 3 H 3 P

oss c \] rft (Mojc \ i-PO os ®> φ O CQ O> Φ ft

\ H 3 1 \ H

ΗΛί-Ρ Φ τ) H S3 Ο ΟΦΦ Si -Ρ Ο Φ> ϋ S -0S> C5. ® • Η Φ Ό

Lft Η CVJ Ρ S Φ Ρ φ φ Τ3 φ ® • Η Ν Η Η Η Τ3 Φ -Ρ ft Λί 3 φ Φ - ε - ω φ s Φ • Η Φ 0] · Η +5 [Q Φ Φ CQ Φ pH & 0 · Η ιΗ * Ρ

3-S

S S Φ Η «Φ s ~ \ Φ 3 φ · Η ΙΕ> -Ρ I Η 3 ft cd s 3 ft ®

Ό Ό bo Φ Φ ft S

_p - ^ O +3 w Cd

cd ^ S S td ^ P

3ΗΦ Φ05ΗΦ ^ 1 O H +3 O I Ο H cd

3 φ Ο Ο cd S Φ O O

• Η -Η N 3 -Ρ Φ -Η -Η N 3 ® i-pid * p ft-p i-pcd -p bp

Φ Cd ft O S Ο Ο Ο Ο 3 Λ · Φ cd ft Ο S Ο Ο Ο Ο S

• Η 3 Η 01ΛΟΙΑΟ (QOta-HS-H OLftOLftO-H

Η -Ρ Η ο r (\ | ΙΓ \ ΦΟΦ Η · Ρ 8 ο ν CM ΙΛ 3 Ο S · Η w 3 «· Η Ο S · Η ^ ® φ ο 3 to φ ο αΟ 0 3 Φ Φ Η Ο 3 3 -Ρ NOS '-' SP Ρ «η Ο · Η Φ S ε bO ο · Η ®« ^ os Ο Ο Φ ^ Ο S Μ 8203251 25

EXPERIMENT 7 - influence on pH

Oil-in-water emulsions were prepared as described in experiment 5 and their pH values were measured 1 and 7 days after preparation using a pH meter connected to an Ingold electrode.

The following results were obtained: 8203251 26

β S.

(]) Φ 60 & 0 β r- Ο O v- β (Τ 'N O (O' Ό

T3 C \ J CO K \ LPi CO "G COrOJNAOJ

H - - - - - H ** · - * · O O- O 'O' O 'O' O 'O AND CO O' O 'O' O '

O O

IS] N

β T3 Ό

• H * H

β bO β bO

Ο β Ό N Ό CO ΙΛ Ο β oO ^ CT'Od "p TS NO 'IN CO O' β Ό IN CO CO r- O 'P,» ···· * «· ft«. ». ·. · .· H r- O 'O' O 'O' O 'Hr- O' O 'O' OO 'r-

β P

(D Φ

bO M

β β

Co co co co co oo Ό OOOOO

0k 0k 0k 0k 0k ^ ^ ^ ^ ^ H IN 00 00 co 00 CO H IN CT'O'CT'O'iT '° 2 O o

N N

a * +5 Ό Ό a · η · η> ρ <u -p +;

η φ +> <D

g bo β S bO

<i -H β> * rl β

Q Ό O 'O' O '00 CO Ο Ω Ό (\ J OJ CM CM 0J

^ w, οίϋ »·· * · * · * β p. r- OOCOCOCOCO P- r- O 'O' O 'O' O 'β w $ 3 β 2 Φ β

0 P

ti 2

ο P

Ο β β β ω ο φ

η bo S

• Ο β Ο β _ ο 'ό ΏΙΝΏνΟΌ Ο Ό Ο Ο θ' Ο Ο η Ν ► ^ ^ Η ** · «» · *> β IN Ο0 οΟ 00 cO 00 Ο IN O 'O' co O 'O' \ Ό · Ο

Η · Η Η N

Ο β ° ^

> 0> 'G

P \ "« j OJ -P Η β.

N. φ Ο Ο r- S> β * 4 · ^

c \ j S

H β H r rd Ό ^

bO

»· Β ^ β Φ Ό οο οο Ο O 'co Φ Ό -4" cm (Μ cm (Μ. F * ¢, * »#%, f_j *» ·· «» Γ * "(0 r- COCOO' COOO ω r- O 'O' O 'O' O '

Η H

β B

ε £ <D Φ 1 Ss β ft ^ p * Φ t3 Φ Ό +> w -P 'β ^ β ^ ^ Η β & Η Φ I Ο Η I ° β φ Ο Ο βΦΟ ο • Η · Η Ν β · Η · Η C3 β ι -Ρ β -ρ ι -ρ β -ρ Φ β Ό ΟβΟΟΟΟ Φβτο Ο β ο ο ο ο • Η β · Η Ο ΙΛ Ο ΙΓ \ Ο · Η β · Η ΟΙΛΟΙΑΟ Η 4J ε ο r β 1Λ H-ρε β Ϊ - (\ | ΙΛ Ο β · Η - ° g · Η - φ Ο Φ ο ο ο β β £ ρ _ρ 's β -Ρ β Ο · Η - ° 0 -rj Ο β w Ο β 27 β S3 3 <d bo & 0 cd vD KNOOr- «3 OOcOVO-3- H Tf pf · ΙΛ ΙΛ ΙΛ oO Η Ό Ο 't * CM <γ- ^ O r> _ oO CO 00 CO CO OtN O 'On ON O' N 5 CO «rQ Ό * H 'ft

β P

Ο Ο Ο 60 f-ι 60

Q, CO ΟΓΛν ^ οΟ Pi CO ^ w ^ ϋ) I

HTd .4- J- .4- -3 "MO HT3 NO VO CO ®

·> ··> ·· ~ ~ ·· · * · * s CO CO CO CO CO ON (Jn On O 'ON

β P

φ Φ bO & 0 c — ϊ cti H cd

Ο -ΰ Or-OOO 0¾ CM CM CM 04 CM

Q *. «.«. ·. ·. 0 · * · ** “« * NIN O0 CO CO CO CO N IN O 'O' O 'O' O '

CD T3 ^ -P -rt T *

Cd P £ ft

> +3> -P

φφ (OP

fi s ω & § * rl CC · Η CD,, rj Q rjj CM CM CM CM <M Ο βΤί -P "fT \ -S '-3" J "+3 v oO CO CO CO CO -P r- O 'O' O 'ON O' CD WJ ®

cd p. cd P

u P

£ -s β p φ Φ o «p p

O O

ο °

• bO · bO

pj I-4 crt rH rH C5

0 0¾ ΟΟΟνγ-Ο ο Ot3 CM CM O CM CM

·> O · «·. ····.> O - - * * *

\ SC ^ CO CO CO CO CO \ NO. on ON ON ON ON

HP H

0Ό

> -H> * H

P P

IPn O OVJ o (I) 4J bo φ +> yj

• i-l fl) flS * H Φ ClJ

Td g Ό cm cm cm cm · Ρ S j'-S'-Sr-S'-P '-. . r. ·· "·· ·· ··,. R- CO CO CO CO CO - v O 'O' O 'ON O' φ Φ

• Η H

CQ Φ

Η H

P P

e a φ Φ | I ^ ρ ε ft g Φ p4 <D Mi 1 8203251

"P -P" P

cd w cd ^ te / -s 5 ^ 1 Η Φ · H ®

P Ο Η P Ο H

• Η © Ο Ο Ή CD Ο O

I -Η N P J Ή W .ft Q) +> Cd +3 ® 40 Cd _ -P _ _ _ _ • ri cd T3 OPOOOO -H cd Ό opoooo

Η P * r) OLAOITnO Η Ρ · Η Ο 1Λ O uv O

Ojjc υ rCMli \ 0-PB ο Γ CM in P -H ^ P Η "" Ο) o CD O.

OP P ft

✓-> β -p ^ P P

Ο Ο -rl Ό ο · Η

w Ο β —'OP

2 8 β φ 60 β (Λ Ο Ο -4- Ο Η Τί A VO VO Α Ο - - - - - Ο IN ON ON <Α C3N ΟΝ Ν β ΤΙ • Η. Β 0 β 60 Ρη β 4 · Γ · CO CO (Μ Η Τ) (Js Ο On CT \ Ο τ- Ο »Ο θ 'Ο» Ο ν ν

β S.

φ Φ 60 Μ β ΗI <8 τι (Μ Α (Μ Α ΙΛ 0¾ θ 'ΟΝ Ο Ο Ο ρ_ι ·. «·.«. ·> 43 Ο - - - - - ON ON ON O' CΤ 'Ο β Ν Ν CO ΟΟ On ΟΟ ΟΝ ο> β ν φ τι +> β £> Η β ΤΙ „β> · pq 43 Φ ί-ι Φ, ρ 43 60 43 Η 60 φβ β · · β _ £} Β Τ5 -3- -3- -3- ΙΑ ΙΑ β QTI Οτ-ν-ΟΟ • Η *. «**» *. · »Ρ * **" ** 45 p r- (J \ 0 \ (J \ G \ <J \ -P r- CT \ CTn CT \ 0> β a β β P- ® β g 43 β β Ο φ Ο Ο β «ο ·

ϋ r — I W

£ Ο Ρ- S3 α>> g, • 60 \ 60 Η β ΗΗβ _ ^ _ Ο ΤI OJCNJOJfMlA Ο Ο ΤΙ Ο ΟΝ ΟΝ Ο Ο *> pro--> Ο - - - - - \ ON ON ON A ΟΝ ΟΝ Ν Ν Ον ΟΟ C0 ΟΝ Ον Η Ο ΛΙ «β ON \ Τ3> β τ- · Η -Ο β ΙΑ Ή Α Ο β β ρ Ο 60 φ 43 60 • Η β β · Η Φ β _ TJ 43 Τί A - tf- -d "-p- Α ΤΙ S ΤΙ τ-Οί-rr- Q) ·» · »** ·» *> *** »*» · »· * <θ 'θ' θ 'θ' θ '-' τ- ΟΝ ΟΝ ΟΝ Ο ον φ Φ • Η Ή Φ Μ 1-1 ^ 3 s ε ρ Φ

I I

β Β β Β ρ ρ, Φ Ρι 43 ΤΙ 43 Ό β 'β w 3 3 ^ I Η Φ I Η φ β Ο Η β Ο Η • Η Φ Ο Ο · Η Φ Ο Ο I · Η Ν β I · Η Ν β Φ43β 43 Φ 43 β 43

• Η β ΤΙ ΟβΟΟΟΟ · ΗβΤ> OgOOOO

Η β Ή Ο Α Ο Α Ο Η β · Η ο Α Ο Α Ο Ο 43 Β Ο r (¾ Α Ο 43 Β Ο τ-ΓϋΑ β · Η --- g · Η w ρ Ο Φ Ο ο β g β ^ ρ 43 β 43 Ρ Ο · Η 'Η Ο' γΙ - ϋ β - ο β 8203251 29 -p cd

> C

<o Φ

p bD

cd \ o -t co VD U) C3 T3 Ο ΙΛ 4 ΙΓ \ 1Λ 9> · »·» ^

4j 1> ~ O '0 \ O' (Τ 'ON

ns cd

C

-P

c Φ

Ο H

PS o o o O Cd cd Ό • * rl H W C O P- o> u \ ft

H M

• o t>

OJ

60 0 cd r CO (Μ N Ό • Η 'Ο O t- τ ~ r · v crt

v Ο Ο Ο Ο O

- v- r * r- r- r-

Φ H

to

iH

C

s

(D

t ^

U B

Φ ft 4J T3 cd ^ 3 1 H <13

CO H

• Η Φ Ο O

I · Η Cd U

<u -p cd. -p • H cd Ό ocoooo H U -Η Ο ΙΛ O IP o

ο -P B o r CM P

C -H w as ooc · ^ C -P 60 Ο · Η ^ oc 8203251 3 ° D © a results indicate that metronidazole, dimetridazole and ipronidazole at the concentrations tested are of no significance in the pH of the tested affect oil-in-water emulsions.

5 EXPERIMENT 8 - flotation and foaming properties

This experiment is designed (IP 312/74) to determine the flotation and foaming properties of oil-in-water emulsions using the following method:

Oil-in-water emulsions of oil concentrates were prepared according to the method described in Experiment 5, but replacing the distilled water with synthetic hard water (a calcium sulfate solution with a total hardness equivalent to 200-10 ppm expressed as as calcium carbonate, prepared by dissolving 0.344 g of calcium sulfate (CaSO 2 .PH 2 O) per liter of distilled water). 100 ml of the oil-in-water emulsion was placed in a 250 ml graduated cylinder (calibrated according to BS 604: 1952), stoppered and shaken vigorously for 15 seconds. After shaking, the cylinder was placed in a vertical position and the volume of foam and liquid 20 was recorded immediately and 1, 5, 1 and 15 minutes after shaking (a foam may also be formed above the foam, but this foam tends to break down, leaving air pockets and the height of the foam in the cylinder is difficult to determine. The foam, which is denser, can be read easily and the foam level has been recorded for convenience).

Concentrate C formed a precipitate when emulsified using synthetic hard water. This precipitate did not change with the incorporation of metronidazole, dimetridazole or 50 ipronidazole. The experiment was repeated using distilled water instead of synthetic hard water and the results of this dilution of concentrate C with distilled water are given below).

The following results, in which "volume" indicates the volume of foam 35 and liquid, were obtained: 8203251 31 LTs ΟΟΟΟΟ ^ SSSSo χ- ooooo χ- ΟΟΟΟΟ χ- χ- χ- χ- χ- τ-χ-r-x ^^

Id 'β Ο Ο ΟΟΟΟ le'so ΟΟΟΟΟ> ® x- ΟΟΟΟΟ> Φ χ- ΟΟΟΟΟ φ .ρ χ- χ- χ- χ- χ- φ-ρ χ- χ- χ- χ- χ- “g Λ 3 fq η η · ε 6 +5 ν5 4 ^ - '«5« ^

cd Ρ? S

¢. φ Ρ Φ £ u -g yy φ = ϊ LA ΟΟΟΟΟ Φ51Λ ΟΟΟΟΟ οΦ ΟΟΟΟΟ Ο Φ ΟΟΟΟΟ r- ν * τ- r * r- Ρη £ * r * v ”V“ ^ ”T“ Ο 0 ο «ΰ ° 2 C Η * *,

• I J

Η Η ο Φ ο φ> ε> ε Ο Ο χ- Οχ-ΟΟχ- Ο £ x- SRooo >> ΟΟΟΟΟ >> ΟΟΟΟΟ χ- χ- χ- xr- χ- X- X- X- X- χ ~ χ - Χ ~ φ φ • Η £ Ό r ** © ® • Η Μ Ο Ο Ο Ο Ο ΙΑ Η Ο ΟΟΟΟΟ. β OJOJCUrUOJ 3 ΙΑ C \ JC \ J ΓΑ ΙΑ g χ- χ— χ— X- Χ ~ ε X- χ- X- X- χ— φ φ I} Μ χ "'® ε ® ε JJ Ο ·' - Ρ Pi Π5 # «3 Ό? Ϊ. ~ C _4 <<> Ρ Η • Η φ Ο Φ · Η Φ Ο Φ I · Η Ο Η I · Η Ο ^ © ++ ν ο ® -ρ 5? • η to φ ρ 'Ί 2 JS h ι — 4 Lt * Ti i — I ^ * 0 4- *

0 + 1 · Η Ο Ρ Ο Ο Ο O O + JfH Ο Ρ Ο Ο Ο O

CP O LA Ο ΙΑ Ο Ρ P 0lAO ^ S

ΦΟ O x- (\ J LA Φ + J O x ~ C \ J LA

o 'P vp + ip ε CO ο Φ Cd ο · Η w ο ε ^ ο "o 8203251 32 ΙΑ Γ ο J · nj Γ ΙΑ Ο LA ΙΑ Ο Ο ν- ΙΛΙΆΙΆΓΛΙΛ ν- -t OJ (Λ ΙΛ Κ \ Γ "Γ * Γ" Γ * Γ "Γ * ίτ Γ * Γ" -Ρ -Ρ

Jl Λ ο ΛΙ (\ | οο 4 Γ cd Ο Ο Ο Ο Ο ΙΑ> β τ- 4 Λ ΙΛ ΙΛ 4> β r- ΙΑ 4 ΙΑ 4 4 Φ φ TrT - ^ - r * Φ φ τ ~ vr ~ v τ 'Ρ Ρ Ρ -Ρ 2 2 η a pc * Η · Η

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These results demonstrate that the incorporation of metronidazole, dimetridazole or ipronidazole at the indicated concentrations does not make a substantial difference to the flotation and foaming properties of the oil-in-water emulsions under investigation.

The following example illustrates metalworking concentrates which, after appropriate dilution with water, are suitable for the preparation of metalworking fluids of the present invention.

EXAMPLE

10 A suspension is prepared by microfine dimetridazole (25 w / v vol.), Texofor M6 (if w / v. Vol.), Arylan CA (6 w / v. Vol.), Attagel 50 (1.0 wt. / vol · #) and petrol (odorless) to 100 vol * $. One liter of this concentrate is mixed with 99 liters of a general purpose cutting oil concentrate to obtain 100 liters of a cutting oil concentrate containing 2500 ppm dimetridazole. This concentrate (100 liters) can be used with 2if00 liters. dilute water to obtain 2500 liters of metal working fluid containing 100 ppm dimetridazole.

8203251

Claims (15)

A method for combating industrial decay of liquid organic materials containing water or aqueous liquids containing organic materials caused by obligate anaerobic sulfate reducing bacteria, characterized in that the aqueous phase of liquid organic materials containing water or aqueous liquids containing organic materials incorporating an amount of one or more nitroimidazole compounds selected from the group consisting of dimetridazole, metronidazole, secnidazole and ipronidazole in an amount sufficient to oblige the growth of anaerobic prevent sulphate-reducing bacteria. 2. Process according to claim 1, characterized in that as liquid organic materials containing water of5 or aqueous liquids containing organic materials, petroleum hydrocarbons or vegetable oils containing water or aqueous liquids containing petroleum hydrocarbons or vegetable oils contain, used in industry, used « Process according to claim 1 or 2, characterized in that as liquid organic materials containing water or aqueous liquids containing organic materials, fuel oils, lubricating oils, mineral oil-based hydraulic fluids, oil-in-water emulsions, water-in-oil emulsions, aqueous solutions and emulsions of glycols, which are used as metal working fluids, paper pulp sulfur processing fluids, water based paints, oil well injection water, industrial process water, electrolytic coating solutions , sealed water circulation systems, hot water storage and dispensing systems and gas container water seals used for the storage of hydrocarbon gases. 4. Process according to claim 3, characterized in that metalworking fluids are used as oil-in-water emulsions. 5. Process according to claim 3, characterized in that hydraulic fluids of the water-in-oil emulsion type are used as water-in-oil emulsions. 6. Process according to one or more of claims 1 to 5, characterized in that a solution, suspension ifO or emulsion containing one or more nitroimidazole compounds, 8203251 I & selected from the group consisting of nit dimetridazole, metronidazole, secnidazole and ipronidazole and water, glycols, ethyl oxalate, dimethylformamide, dimethylacetamide or liquid hydrocarbons or mixtures thereof and, if necessary, add one or more surfactants to liquid organic materials containing water, or aqueous liquids, which contain organic materials Process according to one or more of claims 1 to 6, characterized in that an amount of a 10 or more nitroimidazole compounds selected from the group consisting of dimetridazole, metronidazole, secnidazole and ipronidazole is included in the aqueous phase of liquid organic materials containing water or aqueous liquids containing organic materials from 100 ppm to 500 ppm of the total volume of the liquid organic materials containing water or the aqueous liquids containing organic materials. Process according to one or more of claims 1 to 6, characterized in that an amount of one or 20 more nitroimidazole compounds selected from the group consisting of dimetridazole, metronidazole, secnidazole and ipronidazole is included in the aqueous phase of liquid organic materials containing water or aqueous liquids containing organic materials from 100 ppm to the total volume of the liquid organic materials containing water or the aqueous liquids containing organic materials. 9. Process according to one or more of claims 1 to 8, characterized in that one or more nitroimidazole compounds selected from the group consisting of dimetridazole, metronidazole, secnidazole and ipronidazole together with one or more known means for combating industrial decay of liquid organic materials containing water or using aqueous liquids containing organic materials. 10. A process according to claim 9, characterized in that one or more compounds of the group p-chloro-m-cresol, phenol, heavy metals and compounds releasing formaldehyde are used as known raw materials. Method according to one or more of claims 1 to 10, characterized in that the obligate anaerobic sulphate IfO reducing bacteria is one or more bacteria of the group 8203251: W:; K 'Desulfovibrio desulfuricans. Desulfovibrio gigas and Desulfotomacuium nigrificans. to be. 12. Process according to one or more of claims 1 to 11, characterized in that dimetridazole is used as nitroimidazole compound. Process according to one or more of claims 1 to 11, characterized in that the nitroimidazole compound used is metronidazole. 1lf. Metalworking concentrates, which, after appropriate dilution with water, are suitable for the preparation of metalworking fluids, characterized by the presence of oils and / or glycols, emulsifying agents and corrosion inhibitors, which are customary in concentrates used for the preparation, by dilution with water , of metalworking fluids and an amount of one or more nitroimidazole compounds selected from the group consisting of dimetridazole, metronidazole, secnidazole and ipronidazole, which is sufficient to give a concentration of nitroimidazole compounds in the metalworking liquid after dilution with water, which is sufficient for growth of obligate anaerobic sulphate reducing bacteria. Metalworking concentrates according to claim H, characterized in that the amount of nitroimidazole compounds contained in the concentrates is from 0.05 to 5% w / v. Metalworking concentrates according to claim 1 or 15, 25, characterized in that the nitroimidazole compound is dimetridazole. Metalworking concentrates according to Claim 1 or 15, characterized in that the nitroimidazole compound is metronidazole. . * * * * * * 8203251